Two Shared Icosahedral Metallacarboranes through Iron: A Joint Experimental and Theoretical Refinement of Mössbauer Spectrum in [Fe(1,2-C 2 B 9 H 11 ) 2 ]Cs.

Mössbauer and X-ray photoelectron spectroscopies (XPS) are complemented with high-level quantum-chemical computations in the study of the geometric and electronic structure of the paramagnetic salt of the metallacarborane sandwich complex [Fe(1,2-C 2 B 9 H 11 ) 2 ]Cs = FeSanCs. Experimental 57 Fe isomer shifts and quadrupole splitting parameters are compared with the theoretical prediction, with good agreement. The appearance of two sets of Cs(3d) doublets in the XPS spectrum, separated by 2 eV, indicates that Cs has two different chemical environments due to ease of the Cs (+) cation moving around the sandwich complex with low-energy barriers, as confirmed by quantum-chemical computations. Several minimum-energy geometries of the FeSanCs structure with the corresponding energies and Mössbauer parameters are discussed, in particular the atomic charges and spin population and the surroundings of the Fe atom in the complex. The Mössbauer spectra were taken at different temperatures showing the presence of a low-spin Fe atom with S = 1/2 and thus confirming a paramagnetic Fe III species.